CN106179229A - Bombyx mori L. base micropore carbon material and preparation method and application is modified on a kind of high-ratio surface basic anhydride surface - Google Patents
Bombyx mori L. base micropore carbon material and preparation method and application is modified on a kind of high-ratio surface basic anhydride surface Download PDFInfo
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- CN106179229A CN106179229A CN201610812098.XA CN201610812098A CN106179229A CN 106179229 A CN106179229 A CN 106179229A CN 201610812098 A CN201610812098 A CN 201610812098A CN 106179229 A CN106179229 A CN 106179229A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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Abstract
The invention discloses a kind of high-ratio surface basic anhydride surface and modify Bombyx mori L. base micropore carbon material and preparation method and application.Bombyx mori L. is mixed with water swelling postlyophilization, Bombyx mori L. after lyophilizing is prepared as carbonization Bombyx mori L. under protection gas；Carbonization Bombyx mori L. and KOH are mixed; protective gas is carried out activate reaming reaction; high-ratio surface Bombyx mori L. base micropore carbon material is obtained after cleaning the most again, be centrifuged and drying; centrifugal, drying after being mixed with the stirring of this material by metal salt solution again, is passed through oxygen and prepares plasma modification basic anhydride surface modification Bombyx mori L. base micropore carbon material.This materials application delays controlled release aspect in pesticide.The present invention at high temperature utilizes protection gas condition that Bombyx mori L. is carried out carbonization and activation processing; the modification of basic anhydride surface is carried out by the way of infusion process and plasma modification; obtained Carbon Materials has higher specific surface area and basic sorbent site, has higher adsorption capacity and preferable slow-releasing and controlled-releasing action to pesticide.
Description
Technical field
The invention belongs to Carbon Materials technical field, be specifically related to basic surface and modify Bombyx mori L. base micropore carbon material and preparation thereof
Method and application.
Background technology
Pesticide can efficiently control disease, worm, grass and the harm to crops of other harmful organisms, and it is as chemical prevention
Important means, agricultural production plays irreplaceable effect.But, pesticide the most a small amount of in special time can arrive
Reach crop target site, and major part pesticide is directly released in natural environment and causes pesticide utilization ratio low.This part is not
The pesticide playing drug effect can cause Practice for Pesticide Residue in Agricultural Products to exceed standard, many negative to the injury of non-target organism and environmental pollution etc.
Face problem.How to be effectively improved the utilization ratio of pesticide and Targeting delivery function is urgently to be resolved hurrily main of current pesticide field
One of problem.
Slow controlled-release technology is that one can make pesticide activity component slowly release within preset time by physically or chemically means
It is put in target site, and makes drug level maintain the Novel medicine feeding technology of more than valid density in a long time.Biology is many
Hole charcoal is one of material with preferably absorption, and Bombyx mori L. base charcoal derives from the main garbage Bombyx mori L. in Bombyxmori Linnaeus industry, its
The most arbitrarily abandon in rural area and cause environmental pollution, from Electron microscope observe understand Bombyx mori L. have natural three-dimensional drape structure and
Phosphorus content is high, can obtain high-ratio surface multiporous biological charcoal through high temperature cabonization and activation, and its surface is possibly together with abundant N (O)
Group, by promoting its slow controlled release ability to its modification.
Summary of the invention
It is an object of the invention to provide a kind of high-ratio surface basic anhydride surface modify Bombyx mori L. base micropore carbon material and
Preparation method and application.The present invention recarbonizes after first Bombyx mori L. being carried out swelling expanding treatment, then utilizes noble gas to protect at high temperature
Protect and Bombyx mori L. after lyophilizing is carried out activation processing, then impregnated by metal salt solution, dry and plasma surface modification, obtained
Carbon Materials there is higher specific surface area and basic sorbent site, pesticide can be had higher adsorption capacity and preferably slow controlled release
Effect.
The purpose of the present invention is achieved through the following technical solutions:
It is three dimensional pore structures that Bombyx mori L. base micropore carbon material is modified on the high-ratio surface basic anhydride surface of the present invention, its
Langmuir specific surface area is 1000-1300m2/ g, total pore volume is at 0.4-0.6cm3/ g, wherein micropore specific area and pore volume account for
To total specific surface area and more than the 80% of pore volume.
The high-ratio surface Bombyx mori L. base Microporous Carbon of the present invention prepares the preparation method of material, comprises the steps:
(1) Faeces bombycis mixes swelling postlyophilization with water, then by Bombyx mori L. after lyophilizing at N2, in the protective gas such as Ar gas
By high temperature cabonization reaction preparation carbonization Bombyx mori L.；
(2) carbonization Bombyx mori L. and KOH are mixed, carry out activating reaming reaction in protective gas, clean the most again, centrifugal with
And obtain high-ratio surface Bombyx mori L. base micropore carbon material after drying.Clean and use dilute hydrochloric acid and deionized water rinsing to obtain Gao Bibiao 3 times
Face Bombyx mori L. base micropore carbon material；
(3) by high-ratio surface Bombyx mori L. base micropore carbon material, (cation is Fe with metal salt solution3+、Cu2+、Ag+Deng) vibration
Centrifugal drying after mixing, then O2Put into plasma reactor under atmosphere and carry out surface modification, the input voltage of plasma device
20～30V, modification time 10～20min；Modified deionized water cleaning, drying obtains high-ratio surface basic anhydride surface
Modify Bombyx mori L. base micropore carbon material.
Further preferred as scheme, step (1) Faeces bombycis and water mixing plastid are than for 1:100～200, mixing temperature
Being 30～50 DEG C, incorporation time is 0.5～3h.Freezing dry process is first precooling 2～4h under-25 ° DEG C～-20C, then
It is cooled to-60 DEG C～-40 DEG C of lyophilizing 24～72h.
Further preferred as scheme, in step (1), after lyophilizing, the carburizing temperature of Bombyx mori L. is at 700-1000 DEG C, during reaction
Between 2～4h.
Further preferred as scheme, the mass ratio that in described step (2), KOH mixes with carbonization Bombyx mori L. is (6-1): 1.
Further preferred as scheme, described reaming reaction temperature is 650～950 DEG C, and the response time is 0.5～5h.
Optimum reaction condition be reaming reaction temperature be 750～850 DEG C, the response time is 2～3h, and activation temperature have to be lower than carbon
Change temperature, to ensure that the temperature that the carbon skeleton pattern of formation is too high when will not be activated in carbonisation is destroyed again.
Further preferred as scheme, the feed liquid of Bombyx mori L. base micropore carbon material and metal salt solution in described step (2)
Ratio is 1:100～150；Metal salt solution cationic is Fe3+、Cu2+、Ag+Metal salt solution, concentration is 0.1～3.0mol/
L, vibration mixing rotating speed 100～200r/min, vibration mixing temperature 30～60 DEG C, incorporation time 6～24h.Centrifugal drying temperature
Being 100～200 DEG C, drying time is 2～12h.
Optimal parameter be metal salt solution concentration 0.1～3.0mol/L, dipping incorporation time when being 12～18h, is dried
Temperature is 140～180 DEG C, and drying time is 4～8h.At this moment the effect of Bombyx mori L. base charcoal material surface adsorbing metal salt is best.
The high-ratio surface basic anhydride surface of the present invention is modified Bombyx mori L. base micropore carbon material and be can be applicable to medicine sustained and controlled release
Aspect, particularly pesticide delay controlled release aspect.
Products application of the present invention delays controlled release field at pesticide, uses this material to adsorb anabasine pesticide Diacloden, absorption
Load capacity can reach more than 500mg/g, and can prepare slow release effective time 15～delay controlled release farm chemical carrier in the range of 60 days (to release
Put total amount 90% Diacloden as endpoint calculation).
The principle of the invention: the special macromolecular structure being had due to Bombyx mori L. can occur limited swelling to make in aqueous
With, swelling rear volume can increase 1～20 times, and by substep lyophilization, freezing pretreatment, swelling rear Bombyx mori L. can be made Bombyx mori L.
Fluffy macromolecular structure when keeping swelling, then lyophilizing ensure that fully being dried of Bombyx mori L., and consolidates its structure further, can prolong
The specific surface area and porosity of Bombyx mori L. base Carbon Materials after long Bombyx mori L. carbon skeleton raising carbonization-activation.Application impregnation method is at Bombyx mori L. base
Charcoal material surface adsorbing metal salt, then formed at this material surface under the conditions of oxygen-enriched atmosphere by the way of plasma modification
Basic anhydride (metal-oxide) are modified.
In conventional pesticide molecule mostly containing polar group (carboxyl, carbonyl, sulfur-bearing and containing cl radical etc.), and this portion
Polarity group is also the dominant reactive part in pesticide, the suction that these polar groups can be formed with Bombyx mori L. neutral and alkali oxide
Attached position combines.Bombyx mori L. base Carbon Materials just can be adjusted by controlling Bombyx mori L. metal salt solution dipping and plasma modification condition
Basic sorbent site power and quantity, and then just can regulate and control the absorption affinity of pesticide and Carbon Materials, reach the slow-releasing and controlled-releasing action to pesticide.
Plasma refers to ionized gas, and it is the molecular collection of grain such as electronics, ion, atom, molecule or free radical
Zoarium, these are all as lively as a cricket reactive species.In plasma, particle can destroy between original material molecule and combine bond energy, and
Material Middle molecule and plasma intermediate ion is made to be combined into new chemical bond, and owing to its energy is penetrated far below high-energy radioactive
Line, thus plasma pertains only to the surface of material, does not affect the bulk properties of material, and plasma modification has efficiently, ring
Protect, the advantage such as easily controllable, easy to operate.
Compared with prior art, the present invention is advantageous in that:
1. the raw materials used Bombyx mori L. of the present invention has native three dimensional pleated structure and containing a large amount of carboxyls, hydroxyl and amino base
Group, uses KOH high-temperature activation carbonization Bombyx mori L. under protective gas, can form high-ratio surface micropore knot on carbonization Bombyx mori L. surface
Structure, obtains the relatively high-adsorption-capacity to pesticide by the microcellular structure of high-ratio surface；And carry out under the voltage conditions of 20～30V
Modification, is effectively increased basic anhydride reaction of formation speed.
2. by Bombyx mori L. swelling action can in the case of not changing Bombyx mori L. polymer configuration by Bombyx mori L. volume increase 1～
20 times, its internal structure is fixed by cryodesiccated mode by swelling rear Bombyx mori L., Bombyx mori L. base after carbonization-activation can be improved
The porosity of Carbon Materials and specific surface area.
3. after being impregnated slaine by plasma mode, Bombyx mori L. base Carbon Materials is modified, at O2Oxygen molecule under atmosphere
It is ionized as gas ions oxygen atom, and forms metal-oxide with slaine effect, owing to selecting metal-oxide all to have alkali
Property position, so material surface formed alkaline oxygenated position absorption.The using plasma modified-reaction time short (within 30min),
Plasma modification temperature low (less than 200 DEG C), with conventional high-temperature method for calcinating ratio (2～6h, 400～600 DEG C), has substantially
Advantage, and the method reduce high temperature O2To the consumption of C, atom N in material, not only improve product yield but also ensure material list
Face pattern and specific surface area.
4. by the quantity of the controlling factors Bombyx mori L. surface alkalinty adsorption potential such as plasma modification and slaine immersion condition and
Kind, owing to basic sorbent site can produce material impact to the absorption affinity between pesticide and material, therefore passes through plasma modification
And the absorption affinity between slaine immersion condition controllable Bombyx mori L. base Carbon Materials and pesticide molecule, reach pesticide is delayed the mesh of controlled release
's.
5. the carburizing temperature to be less than of activation temperature used by the present invention, to ensure Bombyx mori L. base charcoal material surface N (O) group number
The control of amount and the guarantee of Bombyx mori L. base Carbon Materials support frame stability.
6. the material prepared by the present invention is used for adsorbing anabasine pesticide Diacloden, and its adsorbance can reach 500mg/g
Above, slow-release time sustained-release pesticides carrier in the range of 15～60 days can be prepared by regulation and control carburizing temperature (total with release
Measure 90% Diacloden as endpoint calculation).
Accompanying drawing explanation
Fig. 1 is Faeces bombycis section electron-microscope scanning figure.
Fig. 2 is Bombyx mori L. section electron-microscope scanning figure after swelling lyophilizing.
Fig. 3 is Bombyx mori L. inner surface electron-microscope scanning figure after swelling lyophilizing.
Fig. 4 is that Bombyx mori L. base micropore carbon material electron-microscope scanning figure is modified on embodiment 1 high-ratio surface basic anhydride surface.
Fig. 5 difference slow-release material load capacity curve.
Fig. 6 difference slow-release material slow release release profiles.
Detailed description of the invention
The present invention will be further described with embodiment below in conjunction with the accompanying drawings, but the scope of protection of present invention is not
It is confined to the scope of embodiment statement.
Embodiment 1
The preparation method of Bombyx mori L. base micropore carbon material is modified on a kind of high-ratio surface basic anhydride surface, including walking as follows
Suddenly,
(1) Faeces bombycis and deionized water is more swelling, at 30 DEG C after swelling 3.0h than carrying out mixing for 1:100 according to plastid
Bombyx mori L. is pulled out and carries out lyophilization, first at-20 DEG C of freezing pretreatment 4h, then reduce temperature and obtain lyophilizing to-60 DEG C of lyophilizing 24h
Rear Bombyx mori L..
At N2Bombyx mori L. after 10.0g lyophilizing is raised to 700 DEG C with the heating rate of 5 DEG C/min by atmosphere, and protects at 700 DEG C
Cool to room temperature after holding more than 2.0h, prepare carbonization Bombyx mori L..
(2) by carbonization Bombyx mori L. and KOH2Mix with mass ratio 1:1, at N2Atmosphere is raised to the heating rate of 5 DEG C/min
650 DEG C, and keep 5.0h to carry out reaming reaction at 650 DEG C, after being naturally down to room temperature, gained solid is dissolved in 1mol/L
HCl in clean and dissolve KOH, re-use deionized water and clean to centrifugal after pH ≈ 7, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface Bombyx mori L. base micropore carbon material.
(3) by Bombyx mori L. base multi-stage porous Carbon Materials and 0.1mol/L Fe2(NO3)3Solution is more mixed than 1:100 vibration according to plastid
After conjunction, rotating speed 100r/min, temperature 30 DEG C, incorporation time 6h, centrifugal drying, dries temperature 100 DEG C, drying time 2h.
(4) after drying being impregnated, material 1.0g puts in plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 20V, modification time 20min, after modified deionized water clears up 3 times, cold drying obtains Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material.
Embodiment 2
(1) Faeces bombycis and deionized water is more swelling, at 35 DEG C after swelling 2.5h than carrying out mixing for 1:120 according to plastid
Bombyx mori L. is pulled out and carries out lyophilization, first at-20 DEG C of freezing pretreatment 3h, then reduce temperature and obtain lyophilizing to-55 DEG C of lyophilizing 36h
Rear Bombyx mori L..
In an ar atmosphere Bombyx mori L. after 10.0g lyophilizing is raised to 800 DEG C with the heating rate of 5 DEG C/min, and protects at 800 DEG C
Cool to room temperature after holding more than 2.0h, prepare carbonization Bombyx mori L..
(2) by carbonization Bombyx mori L. and KOH2Mix with mass ratio 1:2, at N2Atmosphere is raised to the heating rate of 5 DEG C/min
750 DEG C, and keep 4.0h to carry out reaming reaction at 750 DEG C, after being naturally down to room temperature, gained solid is dissolved in 1mol/L
HCl in clean and dissolve KOH, re-use deionized water and clean to centrifugal after pH ≈ 7, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface Bombyx mori L. base micropore carbon material.
(3) by Bombyx mori L. base multi-stage porous Carbon Materials and 1.0mol/L Fe2(NO3)3Solution is more mixed than 1:120 vibration according to plastid
After conjunction, rotating speed 150r/min, temperature 40 DEG C, time 8h, centrifugal drying, dries temperature 120 DEG C, drying time 4h.
(4) after drying being impregnated, material 1.0g puts in plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 22V, modification time 18min, after modified deionized water clears up 3 times, cold drying obtains Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material.
Embodiment 3
(1) Faeces bombycis and deionized water is more swelling, at 40 DEG C after swelling 2.0h than carrying out mixing for 1:140 according to plastid
Bombyx mori L. is pulled out and carries out lyophilization, first at-25 DEG C of freezing pretreatment 2h, then reduce temperature and obtain lyophilizing to-50 DEG C of lyophilizing 48h
Rear Bombyx mori L..
At N2Bombyx mori L. after 10.0g lyophilizing is raised to 850 DEG C with the heating rate of 5 DEG C/min by atmosphere, and protects at 850 DEG C
Cool to room temperature after holding more than 3.0h, prepare carbonization Bombyx mori L..
(2) by carbonization Bombyx mori L. and KOH2Mix with mass ratio 1:3, at N2Atmosphere is raised to the heating rate of 5 DEG C/min
800 DEG C, and keep 3.0h to carry out reaming reaction at 800 DEG C, after being naturally down to room temperature, gained solid is dissolved in 1mol/L
HCl in clean and dissolve KOH, re-use deionized water and clean to centrifugal after pH ≈ 7, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface Bombyx mori L. base micropore carbon material.
(3) by Bombyx mori L. base multi-stage porous Carbon Materials and 1.5mol/L Cu (NO3)2Solution according to plastid than 1:150 vibration mixing,
After rotating speed 150r/min, temperature 40 DEG C, time 12h, centrifugal drying, dries temperature 150 DEG C, drying time 6h.
(4) after drying being impregnated, material 1.0g puts in plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 24V, modification time 16min, after modified deionized water clears up 3 times, cold drying obtains Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material.
Embodiment 4
(1) Faeces bombycis and deionized water is more swelling, at 40 DEG C after swelling 1.5h than carrying out mixing for 1:160 according to plastid
Bombyx mori L. is pulled out and carries out lyophilization, first at-25 DEG C of freezing pretreatment 2.5h, then reduce temperature and frozen to-40 DEG C of lyophilizing 72h
Bombyx mori L. after dry.
In an ar atmosphere Bombyx mori L. after 10.0g lyophilizing is raised to 900 DEG C with the heating rate of 5 DEG C/min, and protects at 900 DEG C
Cool to room temperature after holding more than 3.0h, prepare carbonization Bombyx mori L..
(2) by carbonization Bombyx mori L. and KOH2Mix with mass ratio 1:4, at N2Atmosphere is raised to the heating rate of 5 DEG C/min
850 DEG C, and keep 2.0h to carry out reaming reaction at 850 DEG C, after being naturally down to room temperature, gained solid is dissolved in 1mol/L
HCl in clean and dissolve KOH, re-use deionized water and clean to centrifugal after pH ≈ 7, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface Bombyx mori L. base micropore carbon material.
(3) by Bombyx mori L. base multi-stage porous Carbon Materials and 2.0mol/L Cu (NO3)2Solution according to plastid than 1:100 vibration mixing,
After rotating speed 200r/min, temperature 50 C, time 16h, centrifugal drying, dries temperature 200 DEG C, drying time 8h.
(4) after drying being impregnated, material 1.0g puts in plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 26V, modification time 14min, after modified deionized water clears up 3 times, cold drying obtains Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material.
Embodiment 5
(1) Faeces bombycis and deionized water is more swelling, at 45 DEG C after swelling 1.0h than carrying out mixing for 1:180 according to plastid
Bombyx mori L. is pulled out and carries out lyophilization, first at-20 DEG C of freezing pretreatment 4h, then reduce temperature and obtain lyophilizing to-45 DEG C of lyophilizing 60h
Rear Bombyx mori L..
At N2Bombyx mori L. after 10.0g lyophilizing is raised to 950 DEG C with the heating rate of 5 DEG C/min by atmosphere, and protects at 950 DEG C
Cool to room temperature after holding more than 4.0h, prepare carbonization Bombyx mori L..
(2) by carbonization Bombyx mori L. and KOH2Mix with mass ratio 1:5, at N2Atmosphere is raised to the heating rate of 5 DEG C/min
900 DEG C, and keep 1.0h to carry out reaming reaction at 900 DEG C, after being naturally down to room temperature, gained solid is dissolved in 1mol/L
HCl in clean and dissolve KOH, re-use deionized water and clean to centrifugal after pH ≈ 7, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface Bombyx mori L. base micropore carbon material.
(3) by Bombyx mori L. base multi-stage porous Carbon Materials and 2.5mol/L AgNO3Solution mixes according to plastid than 1:100 vibration, turns
After speed 200r/min, temperature 60 C, time 20h, centrifugal drying, dries temperature 120 DEG C, drying time 8h.
(4) after drying being impregnated, material 1.0g puts in plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 28V, modification time 12min, after modified deionized water clears up 3 times, cold drying obtains Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material.
Embodiment 6
(1) Faeces bombycis and deionized water is more swelling, at 50 DEG C after swelling 0.5h than carrying out mixing for 1:200 according to plastid
Bombyx mori L. is pulled out and carries out lyophilization, first at-20 DEG C of freezing pretreatment 4h, then reduce temperature and obtain lyophilizing to-40 DEG C of lyophilizing 72h
Rear Bombyx mori L..
In an ar atmosphere Bombyx mori L. after 10.0g lyophilizing is raised to 1000 DEG C with the heating rate of 5 DEG C/min, and at 1000 DEG C
Cool to room temperature after keeping more than 4.0h, prepare carbonization Bombyx mori L..
(2) carbonization Bombyx mori L. and KOH are mixed with mass ratio 1:6, at N2Atmosphere is raised to the heating rate of 5 DEG C/min
950 DEG C, and keep 0.5h to carry out reaming reaction at 950 DEG C, after being naturally down to room temperature, gained solid is dissolved in 1mol/L
HCl in clean and dissolve KOH, re-use deionized water and clean to centrifugal after pH ≈ 7, be placed in baking oven and be dried overnight, after drying
Obtain high-ratio surface Bombyx mori L. base micropore carbon material.
(3) by Bombyx mori L. base multi-stage porous Carbon Materials and 3.0mol/L AgNO3Solution mixes according to plastid than 1:100 vibration, turns
After speed 200r/min, temperature 60 C, time 24h, centrifugal drying, dries temperature 180 DEG C, drying time 12h.
(4) after drying being impregnated, material 1.0g puts in plasma reactor, is passed through O2As modified gas, plasma
Reactor according input voltage 30V, modification time 10min, after modified deionized water clears up 3 times, cold drying obtains Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material.
Material properties test:
(1) the Electronic Speculum figure of high-ratio surface Bombyx mori L. base micropore carbon material
Use Japan's Hitachi S-3400N type low power scanning electron microscope to silkworm after Faeces bombycis section, swelling lyophilizing
After husky section, swelling lyophilizing, Bombyx mori L. inner surface and the high-ratio surface basic anhydride surface obtained by the embodiment of the present invention 1 are modified
Bombyx mori L. base micropore carbon material carries out the sign of material surface pattern, as shown in Figure 1, Figure 2, Figure 3, Figure 4.
Fig. 1 and Fig. 2 contrast being understood, after swelling, Bombyx mori L. volume becomes big and internal layer generation large number of orifices gap structure.Fig. 3
It is swelling rear Bombyx mori L. inner surface electron-microscope scanning figure, embodies Bombyx mori L. tridimensional network.Fig. 4 is high-ratio surface basic anhydride table
Bombyx mori L. base micropore carbon material electron-microscope scanning figure is modified in face, it can be seen that the Bombyx mori L. base Carbon Materials after plasma modification can be with shape
Become loose structure.
(2) pore structure study of high-ratio surface Bombyx mori L. base micropore carbon material
Use 3-Flex specific surface pore-size distribution instrument that U.S. Micro company produces to prepared by the present invention with the most swelling
After process Bombyx mori L. and swelling treatment, Bombyx mori L. is that raw material prepares Bombyx mori L. porous carbon material (according to embodiment 5 activation condition), Gao Bibiao
Flour base modified oxide Bombyx mori L. base micropore carbon material and the employing alkaline oxygenated surface of high-temperature calcination are modified and (are selected embodiment 5 to soak
Stain condition) Bombyx mori L. base Carbon Materials pore structure be measured, result is as shown in table 1.
The specific surface area of table 1. Bombyx mori L. base micropore carbon material and pore-size distribution.
Smicro, Vt, and VmicroRepresent the specific surface area that micropore is provided, the pore volume that total pore volume and micropore are provided respectively.
According to 1 column data of table, the Bombyx mori L. base micropore carbon material Langmuir specific surface prepared by six kinds of embodiments
Amass 1000～1300m2/ g, total pore volume is about at 0.4-0.6cm3/ g, wherein micropore specific area and pore volume account for total specific surface area
With pore volume more than 80%.Bombyx mori L. porous carbon material is prepared respectively, its ratio with Bombyx mori L. after non-swelling treatment Bombyx mori L. and swelling treatment
Surface area and porosity have significant difference, and the specific surface area and porosity of the most swelling Bombyx mori L. base Carbon Materials is only swelling rear Bombyx mori L. base
About the 60% of Carbon Materials.The ratio of Bombyx mori L. base micropore carbon material is modified through the surface, alkaline oxygenated position that plasma modification obtains
The data such as surface area and pore volume slightly decline (about about 10%) with for having before modified, illustrate that plasma modification can be to Bombyx mori L.
Base Microporous Carbon surface pore structure has some effects.And use the alkaline oxygenated position face finish material that high-temperature calcination mode obtains
Because high temperature action causes Bombyx mori L., base Microporous Carbon surface pore structure is seriously damaged, and its data such as specific surface area and pore volume are only
About 60% before modified, has a strong impact on its absorption property.This explanation, in embodiments of the invention coverage, prepares institute
The Bombyx mori L. base micropore carbon material obtained is a kind of micropore carbon material with high specific surface area.
(3) different Bombyx mori L. base Carbon Materials constituent contents and product yield are analyzed
Use Japan's Hitachi S-3400N type low power scanning electron microscope energy spectrum analysis, to unmodified Bombyx mori L. base charcoal
Material, the embodiment of the present invention 1～6 and the Bombyx mori L. base obtained by high-temperature calcination modification (selecting embodiment 5 immersion condition) are micro-
After hole Carbon Materials and above-mentioned material ultrasonic cleaning, sample carries out Fe, Cu, Ag elemental composition analysis and product yield compares such as table 2 institute
Show.
The different Bombyx mori L. base Carbon Materials doped chemical of table 2 is containing scale
Knowable to table 2 data, unmodified Bombyx mori L. base Carbon Materials does not contains Fe, Cu and Ag element, after plasma modification
Embodiment 1～6 contains 0.8～1.5% metallic element not etc. respectively, and after ultrasonic cleaning, metallic element does not reduce,
Illustrate that the material after plasma modification is respectively connected to Fe, Cu and Ag element and is firmly combined with, and through high-temperature calcination
After its product yield of material be significantly less than other material, illustrate that plasma modification is better than high-temperature calcination in product yield
Method.
(4) Bombyx mori L. base micropore carbon material sustained release performance is analyzed
The Bombyx mori L. base micropore carbon material of case study on implementation 1,3,5 preparation is carried out pesticide Diacloden absorption carriage amount and slow release is bent
Line analysis, wherein the adsorption conditions of Carbon Materials is that 50mg slow-release material puts into vibration absorption in 50mL 0.8g/L Diacloden solution,
Bath temperature 30 DEG C, vibrate rotating speed 200 revs/min；The slow release condition of Carbon Materials is that after 50mg adsorbs, slow-release material puts into 120mL
In deionized water, changing water 100mL, bath temperature 30 DEG C every day, vibrate rotating speed 200 revs/min, and experimental result is respectively such as Fig. 5, figure
Shown in 6.From figure 5 it can be seen that 3 kinds of slow-release materials all reach 500～560mg/g in absorption 48 hours back loading amounts of Diacloden
Between, and there is no difference between three kinds of materials, illustrate that such material can be protected while having different slow release effect
Hold close adsorption effect.From fig. 6, it can be seen that complete release process respectively 15 days, 30 days and about 60 days (total with release
Measure 90% Diacloden as endpoint calculation), the requirement of different times pesticide slow-release can be met.
The above embodiment of the present invention is only for clearly demonstrating example of the present invention, and not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, can also be made other on the basis of the above description
The change of multi-form or variation.Here without also cannot all of embodiment be given exhaustive.All spirit in the present invention
Any amendment, equivalent and improvement etc. with being made within principle, should be included in the protection domain of the claims in the present invention
Within.
Claims (10)
1. Bombyx mori L. base micropore carbon material is modified on a high-ratio surface basic anhydride surface, it is characterised in that: this material is three-dimensional
Pore structure, its Langmuir specific surface area is 1000～1300m2/ g, total pore volume is at 0.4-0.6cm3/ g, wherein micropore compares table
Area and pore volume account for more than the 80% of total specific surface area and pore volume.
2. high-ratio surface basic anhydride as claimed in claim 1 modify the preparation method of Bombyx mori L. base micropore carbon material, and it is special
Levy and be: comprise the steps,
(1) Faeces bombycis mixes swelling postlyophilization with water, then it is anti-that Bombyx mori L. after lyophilizing passes through in protective gas high temperature cabonization
Carbonization Bombyx mori L. should be prepared；
(2) carbonization Bombyx mori L. and KOH are mixed, carry out activating reaming reaction in protective gas, clean the most again, be centrifuged and dry
High-ratio surface Bombyx mori L. base micropore carbon material is obtained after Gan；
(3) after being mixed with metal salt solution vibration by high-ratio surface Bombyx mori L. base micropore carbon material, centrifugal drying, places into plasma
Reactor according is passed through O2Carry out surface modification, the input voltage 20～30V of plasma device, modification time 10～20min；Modified
Rear cleaning, dries and i.e. can get high-ratio surface basic anhydride surface modification Bombyx mori L. base micropore carbon material.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
It is characterised by: in described step (1), Bombyx mori L. and water mixing plastid ratio is for 1:100～200, and mixing temperature is 30～50 DEG C, mixing
Time is 0.5～3h.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
It is characterised by: in described step (1), freezing dry process is first precooling 2～4h at-25 DEG C～-20C DEG C, then lowers the temperature
To-60 DEG C～-40 DEG C of lyophilizing 24～72h.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
Be characterised by: in step (1) after lyophilizing the carburizing temperature of Bombyx mori L. at 700-1000 DEG C, the response time 2～4h.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
It is characterised by: the mass ratio that in described step (2), KOH mixes with carbonization Bombyx mori L. is 6～1:1.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
It is characterised by: activation reaming reaction temperature have to be lower than carburizing temperature.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
It is characterised by: in described step (2), activation reaming reaction temperature is 650～950 DEG C, and the response time is 0.5～5h.
High-ratio surface basic anhydride the most according to claim 2 modify the preparation method of Bombyx mori L. base micropore carbon material, its
It is characterised by: in described step (3), Bombyx mori L. base micropore carbon material is 1:100～150 with the solid-liquid ratio of metal salt solution；Slaine
Anions in solution is Fe3+、Cu2+、Ag+, metal salt solution concentration is 0.1～3.0mol/L, and vibration mixes 100～200r/
Min, vibration mixing temperature 30～60 DEG C, incorporation time 6～24h；Centrifugal temperature of drying is 100～200 DEG C, and drying time is 2
～12h.
10. high-ratio surface basic anhydride as claimed in claim 1 modify the application of Bombyx mori L. base micropore carbon material, and its feature exists
In: its utilization in terms of pesticide delays controlled release.
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